The History of Ammonia to 2012

Harry Vroomen Vice President, Economic Services The Fertilizer Institute

November 19, 2013

www.tfi.org Presentation Outline

• Nitrogen Before Haber-Bosch Ammonia • Fritz Haber, Carl Bosch, BASF and Anhydrous Ammonia • Haber-Bosch Ammonia Production Starts • Ammonia Production Expands • Nitrogen Demand – Global and U.S. Profile • Importance of Haber-Bosch N (nutrients) to mankind 1770’s - Birth of Modern Chemistry

Joseph Priestly Jan Ingenhousz English Minister Dutch Physician (1733 – 1804) (1730 – 1799)

Discovered the Fundamentals of Photosynthesis

Source: Enriching the Earth, Vaclav Smil, 2001. 1770’s - Birth of Modern Chemistry

Carl Wilhelm Scheele Daniel Rutherford Antoine Laurent Lavoisier Swedish Chemist English Botanist French Chemist (1742 – 1786) (1749 – 1819) (1743 – 1794) “discovered” N named “azote”

First Realization that Nitrogen Makes up Most of the Atmosphere

Source: Smil, 2001. 1800’s - Value of N in Crop Production Demonstrated

Jean-Baptists Boussingault Justin von Liebeg French Chemist German Chemist (1802 – 1887) (1803 – 1873)

Scientific Experiments Left No Doubt About Nitrogen’s Crucial Role in Crop Production!

John Bennet Lawes Joseph Henry Gilbert English Scientist English Chemist (1814 – 1900) (1817 – 1901)

Source: Smil, 2001. Birth of Anhydrous Ammonia – NH3

Claude-Louis Berthollet 1784 – Berthollet becomes aware that the element French Chemist (1748 – 1822) “azote” joins with hydrogen to form ammonia

Georg Friedrich Hildebrand German Professor 1795 –The first failed attempt to combine N and H (1764 - 1816)

More than a dozen chemists 1800’s – Conducted experiments to synthesize ammonia

1900 –Ostwald though he had succeeded in synthesizing ammonia –Tests by Carl Bosch for BASF proved him wrong;

NH3 production was result of contaminants in machine Wilhelm Ostwald German Chemist (1853 – 1932)

Source: Smil, 2001, The Alchemy of Air, Thomas Hager, 2008. Nitrogen Sources: Pre Haber-Bosch

Manures (barnyard and other)

Guano (solidified bird excrement accumulated on subtrop/tropical islands)

Chilean Nitrate (sodium nitrate)

Coke‐Oven Gas (by‐product) Ammonium Sulfate ‐ Coke oven gases produced primarily in the steel industry ‐ Produced by reacting recovered coke oven ammonia with sulfuric acid

Nitrogen Fixation Processes: • Electric Arc Process (1901 –Niagara Falls) Uses electrical current to combine N and oxygen in the air to form nitric oxide (NO) (NO)  Nitric Acid  Calcium Nitrate/Sodium Nitrate

• Cyanamide Process (1907 –Italy) Limestone burned to form calcium oxide; fused with coke in electric furnace  calcium carbide

Calcium carbide (CaC2) reacted with N at high temperature to form calcium cyanamide (CaCN2)

Calcium cyanamide (CaCN2)  ammonia; ammonium phosphates; nitric acid; ammonium nitrate

Source: Smil, 2001. N Production as Guano Extraction, Pre Haber-Bosch 425

400

375

350 1840’s ‐ Guano shipments to England and NY City

325 ‐ mostly from Peru 300 1856 Guano Islands Act 275 Congressional protection was afforded to discoverers of guano deposits off islands & reefs in the Caribbean and Pacific. 250

225

200 Conversion rates: 175

thousand metric tons N 150 1860 & 1870 12% N

125 1880 7% N

100 1890 4% N

75 1900 3% N 1910 & 1913 2% N 50

0 1860 1870 1880 1890 1900 1905 1910 1913

Source: Hager, 2008; Smil, 2001. Chilean Nitrate Production, Pre Haber-Bosch 425

400

375

350 Chilean nitrates first reached 325 the European and American 300 markets in the 1840’s

275

250

225

200

175

thousand metric tons N 150

125

100

0 1860 1870 1880 1890 1900 1905 1910 1913

Source: Smil, 2001. Coke-oven Gas (by-product) AS Production, Pre Haber-Bosch 425

400

375

350

325

300

275

250

225

200

175 thousand metric tons N 150

125

100

0 1860 1870 1880 1890 1900 1905 1910 1913

Source: Smil, 2001. Pre Haber-Bosch N Production, Excluding Ammonia - 1913 425

400

375

350

325

300

275

250

225

200

175

150 thousand metric tons N 125

100

75 Nitrogen Fixation Processes 50

0 Guano Chilean Nitrate Coke‐oven gas AS Cyanamide Electrical Arc

Source: Smil, 2001. Evaluating Haber’s Machine

Heinrich von Brunck August Bernthsen Carl Bosch CEO of BASF BASF Director of Research BASF Chemist

Fritz Haber Global N Production Thousand short tons N 0 50 100 150 200 250 300 350 400 450 500

Chilean nitrate (sodium nitrate) Chile

Germany

Great Britain United 1913 - 0.844 mil. tons N States

Norway

France

Canada 1913

Haber-Bosch Belgium Cyanamide 2% 5%

Italy

Japan By-product 36% Chile 58% Russia

Other

Source: Morrison, 1937. Global N Production Thousand short tons N 0 50 100 150 200 250 300 350 400 450 500

Chile

Germany

Great Britain United 1913 - 0.844 mil. tons N States

Norway 1934 - 1.972 mil. tons N

France

Canada 1934

Belgium Chile 7% Cyanamide Italy 11%

Japan By-product 18% Haber-Bosch Russia 64%

Other

Source: Morrison, 1937. German Haber-Bosch Ammonia Production

2.0 WW II 1939-45

Economic Recovery 1924-29 1.5

Economic Turmoil Hitler Gains Power 1929-38 1.0 Million metric tons ammonia Postwar 0.5 WW I Chaos 1914-18

0.0 1913 1915 1917 1919 1921 1923 1925 1927 1929 1931 1933 1935 1937 1939 1941 1943 1945

Source: Ammonia production data taken from Smil, 2001. U.S. Ammonia Production

2.0 WW II 1921: Atmospheric N Corp. ‐ Syracuse, NY 1939-45 ‐ Modified Haber‐Bosch ‐ 15/40 tons per day 1.5 ‐ Sold for refrigeration Great Depression 1929-41 1928: Allied Chemical ‐ Hopewell, VA ‐ 270 tons per day by 1930 ‐ First to focus on fertilizer 1.0 Million metric tons NH3 WW I Dust Bowl 0.5 1914-18 1931-39

0.0 1910 1915 1920 1925 1930 1935 1940 1945

Source: Nelson, 1990; Data: 1910-1940 - Smil, 2001; 1943-1945 - U.S. Geological Survey. U.S. Ammonia Production 4.5 U.S. emerges from WWII with strongest economy 4.0 Becomes largest global ammonia producer CAGR Accounts for 1/3 of global production growth in 1950's 13.4% 3.5 Set trends for modern day production: ‐ natural gas as hydrogen source ‐ plant location near feedstock and transportation 3.0 ‐ integration of NH3 synthesis with downstream materials

2.5

2.0

Million metric tons NH3 1.5

1.0

0.5

0.0 1945 1946 1947 1948 1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959

Sources: Nelson, 1990; Data, U.S. Geological Survey. U.S. Ammonia Production, 1945-1998 25

Postwar Prosperity, 1945-1973

Growth in nutrient application rates, espec. corn & wheat

10 Million metric tons NH3

5 Adoption of hybrid corn varieties

0 1945 1947 1949 1951 1953 1955 1957 1959 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997

Source: U.S. Geological Survey, IFA, TFI. U.S. Ammonia Production, 1945-1998 25

FSU Ammonia Production Surpasses U.S. in 1981

10 Million metric tons NH3

0 1945 1947 1949 1951 1953 1955 1957 1959 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997

Source: U.S. Geological Survey, IFA, TFI. U.S. Ammonia Production 18

1999-2008 16 High U.S. Natural Gas Prices > 40% drop in Prod Capacity

8 Million metric tons NH3 6

0 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Source: TFI, IFA. CHINA

隨著食品在手，你安心

“With food in hand, you have peace of mind” China – The Great Famine

1,400

1,300 Causes:

1,200 Mao's Great Leap Forward => Including Ag. reforms

1,100 Drought Floods 1,000 Other “Worst mass starvation 900 in recorded history” 800

700

600

500

Midyear Population -Midyear Population Million Estimated Deaths in Millions: - 17 (Zhenghua - endorsed 45 Million people is: 400 The Great Famine by Chinese Gov’t) = 43 Largest U.S. Cities Today! 1958 - 1961 - 30 (Bannister, 1987) In 1958, only 12 countries with 300 - 36 (Yang, 2008) populations > 45 Mil., excl. China - 45 (Dikötter, 2010) 200 - 55 (Xiguang, 2005)

100

0 1950 1952 1954 1956 1958 1960 1962 1964 1966 1968 1970 1972 1974 1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012

Source: Tombstone, Yang Jinsheng, 2008; Mao’s Great Famine, Frank Dikötter, 2010; U.S. Census Bureau. China Ammonia Production, 1941-1960 400

361

300

1958 Population: 646.7 Million! Great Famine

200

thousand metric tons N 125

100

9 0 1941 1942 1943 1944 1945 1946 1947 1948 1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960

Data Source: 1941 and 1957, Dong Gaojie, 1989; 1950 and 1960, Long Xingmao, 1987. China Ammonia Production, 1960-1980 15

12.28 12 1973 - In response to rising demand, China imports 13 large ammonia-urea plants from: USA 1960's - Minister of Chemical Industry: Netherlands Japan 9 10 ammonia plants, mostly medium sized France

2 ammonia plants imported from: Great Britain Italy 6 1 urea plant imported from: Million metric tons N 4.98 Netherlands

0.36 0 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980

Source: Data: Huang Gaoqiang, Beijing University; Information - The Chemical Fertilizer Industry in China: A Review and its Outlook, Wang, Wang, Mai, et al, IFA, 2009. China Ammonia Production, 1980-1991 25

20 0.5 MMT N/year

10 Million metric tons N

0 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991

Data Source: IFA. China Ammonia Production, 1980-1991 25

1991: China Surpasses FSU as the Largest Ammonia Producer

FSU Production 15

10 Million metric tons N

0 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991

Data Source: IFA. Largest Ammonia Producing Countries 45  53.6 MMT Material

Production 30 Increases by

~ 30 MMT NH3!

China 20

Million metric tons N Middle East 15

Russia India 10

USA 5

0 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA. Top 10 Ammonia Producing Countries in 2012 32% 45 394 ammonia plants => 53.6 MMT Material 40

30 China NH3 Production Nearly 4 times > Russian production 25 > next 6 largest producers combined

20 2nd-9th largest = 40% of global production Million Metric Tons N Tons Million Metric 15

0 Egypt Saudi Canada Ukraine Trinidad Indonesia USA India Russia China Arabia

Source: Data - IFA; No. of ammonia plants - Zhang and Huang, 2013 IFA PIT Conference, Oct. 2013. China - Urea Production 30

25 Largest Urea Importers - 1989-1992 Average

0% 5% 10% 15% 20% 25% 30% 35% 40%

China 35.2% 20 USA 9.1%

Vietnam 4.5%

15 Philippines 2.8% China Imports 6.9 MMT material India 2.8%

Million Metric Tons N 10 United Kingdom 2.8%

France 2.6%

0 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA. China - Urea Production 30

Largest Urea Exporters - 2012 27 0% 5% 10% 15% 20%

China 16.2% 24 Russia 11.2%

21 Qatar 9.8% China Exports

Ukraine 8.4% 6.9 MMT material 18 Oman 7.3%

Saudi Arabia 7.2% 15  62 MMT Urea (material) Iran 6.7%  36 MMT Ammonia (2/3) Million Metric Tons N 12

3 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA. China: DAP Production 7 *

* 1997 – 40% of global DAP IMPORTS – 5.6 MMT material 5 * 2012 – 27% of global DAP EXPORTS – 10.7 MMT material Net Difference – 16.3 MMT material 5 O 2 4

3 million metric tons P

1 *

0 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA. China: Phosphate Fertilizer Production

14  26.4 MMT Amm Phos Material  4.9 MMT Ammonia (9%) 12

Share of

10 Global Production 5

O 1992 2012 2 8 DAP 2% 42%

6 MAP 0% 49% million metric tons P

0 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Data Source: IFA. Global Ammonia Production 170

160

150 > 99% of N production today is Haber‐Bosch Synthesis! 140

130

120

110

100 90 Increased 80 by 57 times 70 since WWII 60 Million metric tons NH3

0 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010

Source: 1943-1979: U.S. Geological Survey; 1980-2012: IFA; Smil, 2001. Global Nitrogen Use by Crop, 2010/11

Other 15% Wheat 18%

Sugar Crops 4%

Fiber Crops 4%

Other Cereals 5% Corn 17%

Fruits 6%

Oilseeds 7%

Rice Vegetables 15% 9%

Source: IFA. “Downstream” Nitrogen Fertilizers and Materials from Anhydrous Ammonia

Ammonia Ammonium Nitrate - Solid -Liquor Oxygen Nitric Sodium Carbonate Sodium Nitrate Acid

NH3 Phosphate Rock Nitric Phosphate

Ammonia Nitrogen Solutions

Sulfuric Acid Ammonium Sulfate

Also used to produce Phosphoric Acid Ammonium Phosphates plastics, synthetic fibers and resins, explosives, and numerous other Carbon Dioxide Urea chemical compounds. - Solid -Liquor - Diesel exhaust fluid About 87% for fertilizer! World Nitrogen Fertilizer Use 2011 - 107.9 million metric tons N

Other N 20%

Ammonium Sulfate 3%

Anhydrous Ammonia 4%

Urea Nitrogen Solutions 56% 5%

Ammonium Nitrate 5%

Ammonium Phosphates 7%

Source: IFA. World Nitrogen Fertilizer Use 2011 - 107.9 million metric tons N

China Other 31% 33%

Indonesia 3% Pakistan 3% Brazil India 3% 16% USA 11%

Source: IFA. China - Nitrogen Fertilizer Use 2011 - 33.8 million metric tons N

Other N 7%

Ammonium Phosphates 9%

Other straight N 17%

Urea 67%

Source: IFA. India - Nitrogen Fertilizer Use 2011 - 17.4 million metric tons N

Other N 11%

Ammonium Phosphates 11%

Urea 78%

Source: IFA. Global Nutrient Use, 1930-2011 110

100 India surpasses USA to N P2O5 K2O become #2 in N Use ‐ 1998

90 Breakup of the FSU 80

70 China surpasses USA to become #1 in N Use ‐ 1979 60

40 Million Metric Tons Nutrient

30 N use surpasses P2O5 use – 1960

N use surpasses K2O use – 1956 20 USA: accounts for 35% of Global 10 N Use – 1944

0 1930 1932 1934 1936 1938 1940 1942 1944 1946 1948 1950 1952 1954 1956 1958 1960 1962 1964 1966 1968 1970 1972 1974 1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010

Source: Data from IFA. Growth in Global Nitrogen Use 1999-2011: 23 MMT N

Other 24%

China 43% (9.9 MMT)

Brazil 8% (1.7 MMT)

> 75% India 25% (5.8 MMT)

Source: IFA. U.S. Nitrogen Use by Crop, 2010/11

Other 24%

Fruits Sugar Crops 1% 1% Corn Vegetables 49% 1% Oilseeds 1% Rice 2% Other Cereals 3% Fiber Crops 5%

Wheat 13%

Source: Computed from nutrient application rate data reported by USDA and Commercial Fertilizers, 2011. U.S. Nitrogen Fertilizer Use FY2010/11 - 12.84 million tons N

Other N 14%

Ammonium Nitrate Anhydrous Ammonia 2% 27%

Ammonium Sulfate 2%

Ammonium Phosphates 6%

Urea 22% Nitrogen Solutions 27%

Source: Commercial Fertilizers, 2011, Association of American Plant Food Control Officials and TFI, April 2013.  Applying Anhydrous Ammonia

Side dressing nitrogen solutions  U.S. Consumption of Selected Nitrogen Materials

11 Nitrogen solutions 10

7 urea 6 Anhydrous ammonia

million tons material 5

0 1960 1962 1964 1966 1968 1970 1972 1974 1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010

Source: Commercial Fertilizers, 2011 and earlier issues. U.S. Nitrogen Consumption:1850 – 2010/11

14 13.2 Mil Short Tons N – FY2006/07 * PIK 12

FY1953/54: N use surpassed K2O use for good 8 st FY1958/59: N use surpassed P2O5 use for 1 time

6 million short tons N

4 100 years to grow from 3 thousand to 1 Million Tons!

Source: Historical Statistics of the United States, U.S. Census Bureau; Commercial Fertilizers, various issues. Media Focus Here’s My Plan to Improve Our World — And How You Can Help Bill Gates, Wired.com, Nov. 12, 2013

“These days I get to spend a lot of time trying to advance innovation that improves people’s lives in the same way that fertilizer did.” “… the lives of around half of humanity are made possible by Haber-Bosch nitrogen”

Source: Nature Geoscience, Feature Article, Vol. 1, October 2008. “The Haber-Bosch process has been of greater fundamental importance to the modern world than the airplane, nuclear energy, spaceflight or television". Vaclav Smil, Enriching the Earth, 2001.

Thank You!